Nanocomposites with high thermoelectric figures of merit

ABSTRACT

The present invention is generally directed to nanocomposite thermoelectric materials that exhibit enhanced thermoelectric properties. The nanocomposite materials include two or more components, with at least one of the components forming nano-sized structures within the composite material. The components are chosen such that thermal conductivity of the composite is decreased without substantially diminishing the composite&#39;s electrical conductivity. Suitable component materials exhibit similar electronic band structures. For example, a band-edge gap between at least one of a conduction band or a valence band of one component material and a corresponding band of the other component material at interfaces between the components can be less than about 5 k B T, wherein k B  is the Boltzman constant and T is an average temperature of said nanocomposite composition.

RELATED APPLICATION

This application claims priority as a continuation application to autility application entitled “Nanocomposites With High ThermoelectricFigures of Merit” having a Ser. No. 10/977,363 filed on Oct. 29, 2004,and incorporates this application by reference in its entirety.

FEDERALLY SPONSORED RESEARCH

This invention was made with government support awarded by the NASAunder Grant Numbers NAS3-03108 and NASA-500486. The government hascertain rights in the invention.

BACKGROUND OF THE INVENTION

The present invention is generally directed to thermoelectric materialsand methods for their synthesis and, more particularly, to suchmaterials that exhibit enhanced thermoelectric properties.

Solid-state cooling and power generation based on thermoelectric effectsare known in the art. For example, semiconductor devices that employSeebeck effect or Peltier effect for power generation and heat pumpingare known. The utility of such conventional thermoelectric devices is,however, typically limited by their low coefficient-of-performance (COP)(for refrigeration applications) or low efficiency (for power generationapplications). A thermoelectric figure-of-merit

$\left( {{Z = \frac{S^{2}\sigma}{k}},} \right.$

where S is the Seebeck coefficient, σ is the electrical conductivity,and k is thermal conductivity) is typically employed as the indicator ofthe COP and the efficiency of thermoelectric devices. In some cases, adimensionless figure-of-merit (ZT) is employed, where T can be anaverage temperature of the hot and the cold sides of the device.

Applications of conventional semiconductor thermoelectric coolers arerather limited, as a result of a low figure-of-merit, despite manyadvantages that they provide over other refrigeration technologies. Inpower generation applications, low efficiency of thermoelectric devicesmade from conventional thermoelectric materials with a smallfigure-of-merit limits their applications in direct conversion of heatto electricity (e.g., conversion of waste heat or heat generated byspecially designed sources).

Accordingly, there is a need for enhanced thermoelectric materials, andmethods for their fabrication. More particularly, there is a need forthermoelectric materials exhibiting an enhanced figure-of-merit.

SUMMARY OF THE INVENTION

The present invention is generally directed to nanocompositethermoelectric materials that exhibit enhanced thermoelectricproperties. The nanocomposite materials include two or more components,with at least one of the components forming nano-sized structures withinthe composite material. The components are chosen such that thermalconductivity of the composite is decreased without substantiallydiminishing the composite's electrical conductivity. Suitable componentmaterials exhibit similar electronic band structures. For example, aband-edge offset between at least the conduction bands or the valencebands of the two component materials can be less than about 5 k_(B)T,and preferably less than about 3 k_(B)T, wherein k_(B) is the Boltzmanconstant and T is an average temperature of the nanocompositecomposition.

In one embodiment, the present invention provides a thermoelectricnanocomposite semiconductor composition that includes a plurality ofnano-sized structures formed of a first selected semiconductor material,and a plurality of nano-sized structures formed of another semiconductormaterial intermixed together. The nanosized structures can be, forexample, nanoparticles or nanowires. For example, the structures can beformed of two different types of nanoparticles having average diametersin a range of about 1 nm to about 1 micron, or preferably in a range ofabout 1 nm to about 300 nm, or in a range of about 5 nm to about 100 nm.

In another embodiment, the thermoelectric nanocomposite can include asemiconductor host material and a plurality of nano-sized inclusions(e.g., nanoparticles or nanowires), formed of a semiconductor inclusionmaterial, that are distributed within the host material. Thenanocomposite composition exhibits a band-edge offset between theconduction bands or the valence bands of the host material and theinclusion material at an interface that is less than about 5 k_(B)T,wherein k_(B) is the Boltzman constant and T is an average temperatureof the nanocomposite composition. For example, the band-edge offset canbe in a range of about 1 to about 5 k_(B)T, or in a range of about 1 toabout 3 k_(B)T. An energy minimum of the conduction band or the valenceband of the inclusion material can be preferably less than an energyminimum of a corresponding band of the host material. Alternatively, theenergy minimum of a conduction band or a valence band of the hostmaterial can be less than an energy minimum of a corresponding band ofthe inclusion material.

The terms “nano-sized structure” and “nano-sized inclusion,” as usedherein, generally refer to material portions, such as nanoparticles andnanowires, whose dimensions are equal or preferably less than about 1micron. For example, they can refer to nanoparticles having an averagecross-sectional diameter in a range of about 1 nanometer to about 1micron, or in a range of about 1 nm to about 300 nm, or in a range ofabout 5 nm to about 100 nm. Alternatively, they can refer to nanowireshaving average transverse (cross-sectional) diameter in a range of about2 nm to about 200 nm.

A variety of different materials can be employed to form the componentsof the nanocomposite composition. For example, one component (e.g., hostmaterial) can comprise PbTe or PbSe_(x)Te_(1-x) (where x represents thefraction of PbSe in the alloy of PbTe and PbSe, and can be between 0-1)and the other (e.g., inclusion material) can comprise any of PbSe orPbSe_(y)Te_(1-y). Alternatively, one component can comprise Bi₂Te₃ andthe other can comprise Sb₂Te₃ or Bi₂Se₃, or their alloys. In otherembodiments, one component can be Si and the other Ge. For example, Siinclusions can be embedded in a Ge or a SiGe alloy host. In anotherexample, the host and the inclusion materials can be formed of SiGealloys having different relative concentrations of Si and Ge in the hostmaterial than in the inclusion material. Those having ordinary skill inthe art will appreciate that other materials can also be employed solong as their material properties conform with the teachings of theinvention.

In another aspect, the semiconductor component materials (e.g.,nano-sized inclusions) can be randomly distributed within the composite.Alternatively, the components can be distributed according to a pattern.Further, one or more components (e.g., the host material or theinclusion material, or both) can be doped with a selected dopant, forexample, an n-type or a p-type dopant, with a concentration of, e.g.,about 1 percent. In some embodiments that employ Si and Ge materials,boron is utilized as a p-type dopant while phosphorous is employed as ann-type dopant. Those having ordinary skill in the art will appreciatethat other dopants can also be employed.

In further aspects, the nanocomposite semiconductor material can exhibita reduction in thermal conductivity relative to a homogeneous alloyformed of the component materials by a factor of at least about 2, e.g.a factor in a range of about 2 to about 10. Further, the nanocompositematerial can exhibit a thermoelectric figure of merit (ZT) that isgreater than 1. For example, the figure of merit can be in a range ofabout 1 to about 4.

In another aspect of the invention, the nanocomposite compositionexhibits an electrical conductivity (σ) that differs, if at all, from anelectrical conductivity of a homogeneous alloy formed of the componentmaterials by a factor less than about 4. While in some cases thenanocomposite semiconductor can exhibit an electrical conductivity thatis less than that of the homogeneous alloy, in other cases theelectrical conductivity of the nanocomposite composition can be greaterthan that of the homogeneous alloy. The Seebeck coefficient, S, of thenanocomposites can be comparable or greater than that of the homogeneousalloy. Further, the power factor, defined as S²σ, can be comparable orgreater than that of the homogeneous alloy.

In another embodiment, the invention provides a thermoelectricnanocomposite material that comprises a plurality of nanowires of afirst type formed of a selected semiconductor material intermixed with aplurality of nanowires of a second type formed of another semiconductormaterial. The interfaces between the two types of nanowires exhibit aband-edge discontinuity in any of a conduction band or a valence bandthat can be less than about 5 k_(B)T, or preferably less than about 3k_(B)T, wherein k_(B) is the Boltzman constant and T is an averagetemperature of the nanocomposite composition. For example, one type ofnanowires can be formed of Ge while the other type is formed of Si.While in some embodiments, the nanowires of the first and second typesare randomly disposed relative to one another, in other embodiments theyare disposed in a three-dimensional pattern relative to one another.

In yet another embodiment, the present invention provides ananocomposite material formed of a plurality of stacked nanowirestructures. Each nanowire structure can comprise an outer shell formedof one semiconductor material and an inner core formed of anothersemiconductor material, where an interface of the outer shell and theinner core exhibits a band-edge discontinuity between any of aconduction band or a valence band of the outer shell and a correspondingband of the inner core that is less than about 5 k_(B)T, wherein k_(B)is the Boltzman constant and T is an average temperature of thenanocomposite composition. The outer shell and inner core can form acoaxial nanowire structure having an average diameter in a range ofabout 2 nm to about 200 nm. For example, the core can be formed of Siand the shell of Ge, or vice versa.

In other aspects, the invention provides a thermoelectric nanocompositesemiconductor composition that includes a semiconductor host materialand a plurality of nano-sized inclusions, formed of a semiconductorinclusion materials, that are distributed within the host material,where a band-edge offset between at least one of a conduction band or avalence band of the host material and a corresponding band of theinclusion material at an interface with the host material is less thanabout 0.1 eV.

In another aspect, the present invention provides a method ofsynthesizing a thermoelectric nanocomposite semiconductor compositionthat includes generating a powder mixture comprising two sets ofnano-sized semiconductor structures, and applying a compressive pressureto the mixture while heating it at a temperature and for a time durationchosen to cause compaction of the two sets of nano-sized structures intoa nanocomposite material. The compressive pressure can be, for example,in a range of about 10 to about 1000 MPa. Another way to make thenanocomposites is to add nanoparticles or nanowires with higher meltingpoint into a melt of the host material and agitate the mixture through,for example, induction heat caused fluid mixing.

In a related aspect, compression can be enhanced by heating the mixture,e.g., by causing a current density flow through the compressed mixturefor heating thereof. In general, the current level (e.g., currentdensity) can depend on the sample size. In some embodiments, a currentdensity in a range of a few thousands A/cm² (e.g., 2000 A/cm²) can beemployed.

Further understanding of the invention can be obtained by reference tothe following detailed description in conjunction with the associateddrawings, which are briefly described below.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 schematically depicts a thermoelectric nanocomposite compositionin accordance with one embodiment of the present invention,

FIG. 2A schematically depicts variations of electronic band-edge offsetat interfaces of the host and the inclusion materials in thenanocomposite composition of FIG. 1,

FIG. 2B is a graph illustrating that an energy minimum of the conductionband of n-doped silicon nanoparticles embedded in a germanium hostmaterial can be lower (depending on the stress conditions) than theenergy minimum of the germanium host's conduction band,

FIG. 3 schematically depicts a thermoelectric nanocomposite compositionaccording to another embodiment of the invention in which a plurality ofnanoparticles are distributed according to a three-dimensional patternin a host,

FIG. 4 schematically depicts a nanoparticle having a core portion formedof one semiconductor material surrounded by a shell formed of anothersemiconductor material,

FIG. 5A schematically depicts a thermoelectric nanocomposite materialaccording to another embodiment of the invention, which is formed as amixture of two types of semiconductor nanoparticles,

FIG. 5B schematically depicts a nanocomposite material according to oneembodiment of the invention that includes a plurality of semiconductornanoparticles having core-shell structures,

FIG. 6A schematically depicts a thermoelectric nanocomposite materialaccording to another embodiment of the invention, which is formed of astack of segmented nanowires,

FIG. 6B is a schematic cross-sectional view of a segmented nanowire ofthe composition of FIG. 6A,

FIG. 6C schematically depicts a thermoelectric nanocomposite materialaccording to another embodiment of the invention, formed as plurality ofrandomly stacked segmented nanowires,

FIG. 7A schematically depicts a thermoelectric nanocomposite materialaccording to another embodiment of the invention, formed of a pluralityof randomly stacked coaxial nanowires,

FIG. 7B is a schematic perspective view of a coaxial nanowire of thenanocomposite material of FIG. 7A,

FIG. 8 schematically depicts a thermoelectric nanocomposite materialformed of a plurality of coaxial nanowires disposed in athree-dimensional pattern relative to one another,

FIG. 9 schematically illustrates a vapor phase deposition system forgenerating nanoparticle and nanowires,

FIG. 10 schematically illustrates a plasma compaction apparatus suitablefor synthesizing a thermoelectric nanocomposite material from a mixtureof nanoparticles,

FIG. 11 presents X-ray diffraction data corresponding to two prototypenanocomposite samples according to the teachings of the invention aswell as a silicon sample, a germanium sample, and a sample composed of apowder mixture of silicon and germanium,

FIG. 12 schematically depicts a thermoelectric cooler formed as acascade of thermoelectric modules fabricated by employing thermoelectricnanocomposite materials of the invention, and

FIG. 13 schematically depicts a thermoelectric device for convertingheat to electricity.

DETAILED DESCRIPTION

The present invention is generally directed to thermoelectricnanocomposite materials, and methods for their fabrication, thatgenerally include a mixture of semiconductor nano-sized structures, orsemiconductor nano-sized inclusions embedded in a semiconductor host,that provide a heterogeneous composition. The semiconductor materialsare selected so as to substantially preserve electron transportproperties of the nanocomposite material relative to the host or aputative homogeneous alloy formed of the semiconductor components whilethe heterogeneity of the composition enhances phonon scattering, therebyresulting in an enhanced thermoelectric figure-of-merit, as discussed inmore detail below.

With reference to FIG. 1, a thermoelectric semiconductor composition 10according to one embodiment of the invention includes a hostsemiconductor material 12 (e.g., Ge or SiGe alloy), herein also referredto as a host matrix, in which a plurality of nano-sized inclusions 14(e.g., Si or SiGe alloy of a different Ge concentration than a host alsoformed of a SiGe alloy) are embedded. In this embodiment, the exemplaryinclusions are in the form of substantially spherical particles havingaverage diameters in a range of about 1 nm to about 300 nm, or morepreferably in a range of about 1 nm to about 100 nm, which aredistributed randomly within the host matrix. It should be understoodthat the shape of the nanoparticles 12 is not limited to spherical. Infact, they can take any desired shape. Further, while in someembodiments, the interfaces between the nanoparticles and the host canbe sharp, in other embodiments, an interface can include a transitionregion in which the material composition changes from that of the hostto that of the inclusion.

The nanoparticles 14 are formed of a semiconductor material, herein alsoreferred to as an inclusion material, that has an electronic bandstructure that is similar to that of the host material, as discussed inmore detail below. In this exemplary embodiment, the host materialcomprises germanium or SiGe alloy while the inclusion material issilicon or SiGe alloy. Alternatively, germanium nanoparticles can beembedded in a silicon host. Both the host material and the inclusionmaterial can be doped with a dopant, e.g., an n-type dopant or a p-typedopant. In general, the doping concentration can be optimized fordifferent materials combinations. In some embodiments, the dopingconcentration can be, for example, about 1 percent. In otherembodiments, the host material can be any of SiGe, PbTe, or Bi₂Te₃ whilethe inclusion material can be any of PbSe, PbSeTe or Sb₂Te₃, or viceversa. Other suitable materials can be PbSn, or alloys of PbTeSeSn.Group III-V materials can also be utilized, such as InSb matched toanother material or other materials in accordance with the teachings ofthe invention to other III-V materials. Other examples include HgCdTesystem, Bi and BiSb system. Those having ordinary skill in the art willappreciate that other host and inclusion materials can also be employedso long as their electronic and thermal properties conform to theteachings of the invention, as described in more detail below.

In general, the host and the inclusion materials are selected such thata band-edge offset between the conduction bands or the valence bands ofthe host material and the inclusion material at an interface of the twomaterials is less than about 5 k_(B)T, and preferably less than about 3k_(B)T, wherein k_(B) is the Boltzman constant and T is an averagetemperature of the nanocomposite composition. For example, the band-edgegap can be less than about 0.1 eV.

The concept of a band-edge offset between two adjacent semiconductormaterials is well known. Nonetheless, for further elucidation, FIG. 2Apresents a schematic graph 16 illustrating variation of the conductionband and the valence band energies, and more specifically the changesassociated with the minimum energy of the conduction band and themaximum energy of the valence band, at interfaces of the host materialand the inclusion material in an exemplary thermoelectric semiconductorcomposition according to some embodiments of the invention, such as theabove semiconductor composition 10. The conduction band energies areoffset by an amount 18 while the valence band energies are offset by anamount 20 at interfaces of the host and inclusion materials. As notedabove, in many embodiments, the offset 18 or 20, or both, are less thanabout 5 k_(B)T, wherein k_(B) is the Boltzman constant and T is anaverage temperature of the nanocomposite composition. It should also beunderstood that in some embodiments the nanoparticles can have higherenergy conduction bands, or lower energy valence bands, relative to thehost so long as energy offsets remain small, e.g. within about 5 k_(B)T.Such small band-edge offsets lead to small potential barriers facingelectrons at interfaces of the host and the inclusion materials, therebyminimizing electron scattering at these interfaces. In this manner, theelectrical conductivity of the nanocomposite composition remains closeto that of a putative homogeneous alloy formed from the host and theinclusion materials. For example, the electrical conductivity of thenanocomposite can differ, if any, from that of the putative homogeneousalloy by a factor less than about 4 and in some instances by a factor of3 or 2. While in many embodiments, the electrical conductivity of thenanocomposite composition is less than that of the putative alloy, insome cases, it can be greater.

In some embodiments, the host and the inclusion materials are selectedsuch that the energy extrema of either the inclusion material'sconduction band or its valence band, or both, are lower than theextremum energy of a corresponding band of the host material. Forexample, FIG. 2B presents a graph schematically depicting that theconduction band energy of n-doped silicon nanoparticles embedded in agermanium host material can be lower than the conduction band energy ofthe germanium host.

Although the nanoparticles in the above thermoelectric composition 10are randomly distributed within the host matrix 12, in a nanocompositecomposition 24 according to another embodiment of the invention, shownschematically in FIG. 3, the nanoparticles 14 are embedded in the hostmatrix 12 in accordance with a regular three-dimensional pattern.

In some embodiments of the invention, the nanoparticles 12 are composedof a core formed of one semiconductor material and a shell surroundingthe core, which is formed of another semiconductor material. By of wayof example, FIG. 4 schematically depicts one such nanoparticle 11 havinga silicon core 13 and a germanium shell 15. Alternatively, the core canbe formed of an alloy, e.g., a silicon-germanium alloy, and the shell ofa selected semiconductor material, such as germanium. In otherembodiments, both the core and shell are formed of semiconductor alloys.For example, both the core and shell can be formed of SiGe alloy, butwith different concentrations of Si relative to Ge.

FIG. 5A schematically depicts a thermoelectric nanocomposite composition17 according to another embodiment of the invention that includesnanoparticles of two types (e.g., formed of two different semiconductormaterials) that are intermixed together. Similar to the previousembodiment, the materials of the two types of nanoparticles are chosensuch that they exhibit substantially similar electron properties. Moreparticularly, the materials are selected such that a band-edge offsetbetween the conduction bands or the valence bands of the differentparticle types at interfaces thereof is less than about 5 k_(B)T, orpreferably less than about 3 k_(B)T, wherein k_(B) is the Boltzmanconstant and T is an average temperature of the nanocompositecomposition. For example, a plurality of nanoparticles 19 (depicted withdashed lines) can be formed of Si while the remaining nanoparticles 21are formed of Ge. In other embodiments the nanoparticles 19 and 21 canbe formed of SiGe, PbTe, PbSe, PbSeTe, Bi₂Ti₃ or Sb₂Te₃. For example,one nanoparticle type can be formed of PbSe and other of PbSeTe. Thosehaving ordinary skill in the art will appreciate that othersemiconductor materials can also be employed for forming thenanoparticles 19 and 21 so long as their material properties conformwith the teachings of the invention. Although in FIG. 5A, for ease ofillustration, the nanoparticles of the two types are shown assubstantially spherical with the nanocomposite exhibiting some spatialgaps, in many embodiments of the invention the nanoparticles are denselypacked together potentially resulting in some distortions of theparticles shapes, relative to isolated state, and disappearance of thespatial gaps.

In many embodiments, one or both types of nanoparticles are doped with aselected dopant, e.g., an n-type or p-type dopant. Although thenanocomposite composition 17 is formed of two types of nanoparticles, inother embodiments, a mixture of more than two types of nanoparticles canalso be employed. As noted above, the material properties of thenanoparticles are selected such that the differences, if any, amongtheir electronic band structures are minimal.

In some embodiments, the nanoparticles 19 or 21, or both, can be acore-shell structure such as that shown in FIG. 4 above. For example,the particles 19 can be formed of a silicon core surrounded by agermanium shell. With reference to FIG. 5B, in another embodiment, ananocomposite composition 23 is formed of a mixture of nanoparticles 25that are compacted together, where each nanoparticle has a heterogeneousstructure, e.g., a core-shell structure such as that shown in FIG. 3above. For example, each nanoparticle can have a silicon core and agermanium shell. Alternatively, each nanoparticle can include a SiGecore surrounded by a Si or Ge shell or SiGe alloy with a differentcomposition.

A nanocomposite thermoelectric material accordingly to the teachings ofthe invention, such as the above compositions 10 and 17, advantageouslyexhibit an enhanced thermoelectric figure-of-merit (Z) which can bedefined as follows:

$Z = \frac{S^{2}\sigma}{k}$

where S is the well-known Seebeck coefficient, σ is the electricalconductivity of the composite material, and k is its thermalconductivity. The figure-of-merit Z has the units of inverse Kelvin. Inmany cases, a dimensionless figure-of-merit (ZT), obtained as a productof Z and an average device temperature (T), is employed. A nanocompositethermoelectric composition according to the teachings of the invention,such as the compositions 10 and 17, can exhibit a thermoelectricfigure-of-merit (ZT) that can be greater than about 1. For example, itcan exhibit a thermoelectric figure-of-merit in a range of about 1 toabout 4, or in range of about 2 to about 4. For example, it can exhibita ZT greater than about 1 at room temperature (about 25 C).

Without being limited to any particularly theory, the enhancedthermoelectric properties of nanocomposite materials of the inventioncan be understood as being due to a reduction in phonon thermalconductivity while concurrently preserving electron transportproperties. For example, in the thermoelectric nanocomposite material 10described above, the interfaces between the nano-sized inclusions andthe host material can cause an increase in phonon scattering, therebyreducing the thermal conductivity of the nanocomposite material.However, the small band-edge offset between the host and the inclusionmaterials minimizes electron scattering at these interfaces. Even with asmall reduction of electrical conductivity, the Seebeck coefficient canbe increased such that S²σ would be comparable, or even greater thanthat of a homogeneous alloy formed of the host and inclusion materials.Such a combination of electron-phonon transport properties can lead to abetter thermoelectric figure-of-merit, as can be readily corroborated byreference to the definition of Z above. Particularly, the interfacesbetween the nanoparticles in the above nanocomposite composition 17 canlead to a lowering of thermal conductivity of the composite relative toa putative homogenous alloy formed of the materials of the twonanoparticle types while small differences between the electronic bandstructures of the two materials can substantially preserve electrontransport properties.

In addition, the thermoelectric nanocomposite materials of the inventioncan exhibit enhanced power factors, which can be defined as follows:

power factor=S ²σ

where S is the Seebeck coefficient, and σ is the electrical conductivityof the composite material. For example, power factors in a range ofabout 2×10⁻⁴ W/mK² to about 100×10⁻⁴ W/mK² can be obtained. Withoutbeing limited to any particular theory, the power factor enhancement canbe due to quantum size effects exhibited by the nano-sized components ofthe thermoelectric compositions.

Thermoelectric nanocomposite compositions according to the teachings ofthe invention are not limited to those described above. By way ofexample, FIG. 6A schematically illustrates a thermoelectricnanocomposite composition 26 according to another embodiment of theinvention that includes a plurality of segmented nanowires 28 that arecompacted, in a manner described in more detail below, to form ananocomposite material. With reference to FIG. 6B, each segmentednanowire can include segments 30 formed of one type of semiconductormaterial interleaved with segments 32 formed of another type of asemiconductor material. For example, the segments 30 can be formed ofsilicon while the segments 32 are formed of germanium. Those havingordinary skill in the art will appreciate that other semiconductormaterials can also be employed for forming these segments. In thisexemplary embodiment, the segmented nanowires can have cross-sectionaldiameters in a range of 1 nm to about 300 nm, and more preferably in arange of about 1 nm to about 20 nm. In general, similar to the previousembodiments, semiconductor materials of the segments 30 and 32 areselected so as to minimize differences between their electronic bandstructures. More specifically, in many embodiments of the invention, aband-edge offset between the conduction bands or the valence bands ofthe semiconductor material of the two segment types, at an interface ofthe two materials, is less than about 5 k_(B)T, and preferably less thanabout 3 k_(B)T, wherein k_(B) is the Boltzman constant and T is anaverage temperature of the nanocomposite composition. For example, theband-edge gap can be less than about 0.1 eV.

Although the segmented nanowires 28 in the above nanocompositecomposition 26 are disposed relative to one another in a regularthree-dimensional pattern, in another embodiment 34, shown schematicallyin FIG. 6C, the nanowires 28 are randomly located relative to oneanother.

FIG. 7A schematically illustrates a thermoelectric nanocompositecomposition 36 according to another embodiment of the invention that isformed of a plurality of stacked nanowire structures 38, each of whichis composed of two nanowires disposed substantially coaxially relativeto one another. For example, as shown schematically in FIG. 7B, eachnanowire structure 38 can include an outer shell 40 formed of asemiconductor material that surrounds an inner core 42, which is formedof another semiconductor material. The coaxial nanowire 38 can have across-sectional diameter D in a range of about 1 nm to about 1 micron,or in a range of about 1 nm to about 300 nm, and more preferably in arange of about 1 nm to about 100 nm.

The semiconductor materials for forming the nanowire structures 38 areselected such that an interface of the outer shell and the inner corewould exhibit a band-edge offset between conduction bands or the valencebands of the outer shell and corresponding bands of the inner core lessthan about 5 k_(B)T, wherein k_(B) is the Boltzman constant and T is anaverage temperature of the nanocomposite composition. For example, theband-edge gap can be less than about 0.1 eV.

The heterogeneity of the nanocomposite composition 36, e.g., theinterfaces between the outer shells and the inner cores of the nanowirestructures forming the composition, can increase phonon scattering,thereby reducing the composition's thermal conductivity. The electricalconductivity is, however, less affected because the semiconductormaterials of the outer shells and the inner cores are chosen so as tominimize differences between their electronic band structures. In otherwords, the heterogeneity of the composition can affect phonon scatteringwithout substantially altering electron transport properties, therebyresulting in enhanced thermoelectric properties of the composition.

Although in the above thermoelectric composition the nanowire structuresinclude two layers—an inner core surrounded by an outer shell—in otherembodiments, more than two layers, e.g., two coaxially disposed shellssurrounding an inner core, can be employed. Further, although thecoaxial nanowires 38 in the above composition 36 are disposed randomlyrelative to one another, in another embodiment 44, shown schematicallyin FIG. 8, the coaxial nanowires are arrange relative to one anotheraccording to a three-dimensional pattern.

A variety of techniques can be employed to fabricate thermoelectricnanocomposite compositions according to the teachings of the invention,such as those described above. In general, known techniques, such as,wet chemistry techniques and vapor-liquid-solid condensation, can beutilized to generate the nanostructures, e.g., nanoparticles ornanowires. These nanostructures are preferably incorporated within ahost material, or intermixed with one another, while taking precautionsto avoid generation of interface states, e.g., interface oxides, thatcould contribute to electron scattering, as discussed in more detailbelow. For example, silicon nanoparticles can be treated in an HFsolution to remove any SiO₂ coating formed thereon.

In one method, a host material is impregnated with nanoparticles bytaking advantage of a difference between the melting temperature of thehost and that of the nanoparticles. For example, nanoparticles can beembedded within a host material having a lower melting point than thatof the nanoparticles. Some illustrative examples of such nanoparticlesand host materials include: Si nanoparticles embedded in a Ge host, PbSenanoparticles inside a PbTe host, and Sb₂Te₃ nanoparticles inside aBi₂Te₃ host. Dopants can also be incorporated into the host and thenanoparticles. In some embodiments, dopants can be directly added to thehost. More preferably, dopants can be added to the nanoparticles inaddition to the host.

In many fabrication techniques, nanoparticles and nanowires are utilizedas building blocks for generating nanocomposite materials according tothe teachings of the invention. Hence, exemplary methods for generatingsome exemplary nanoparticles as well as nanowires are described below.Those having ordinary skill in the art will appreciate that similartechniques can be utilized for forming nanoparticles and nanowires ofother materials.

In many embodiments of the invention, nanoparticles, such as Si or Genanoparticles, are synthesized by employing wet chemistry or vapordeposition techniques. Both water-based and non-water-based wetchemistry techniques can be employed. By way of example, Ge nanocrystalscan be synthesized by utilizing a low temperature inverse micellesolvothermal method—a non-water-based technique—that is capable ofyielding gram quantity of Ge nanocrystals. The preparation of Genanoparticles can be performed, for example, in a Parr reactor (e.g.,model 4750, Parr Company, Moline, Ill., USA). A typical exemplaryprocedure for preparing Ge nanospheres can be as follows: 80 mL ofhexane, 0.6 mL of GeCl4, 0.6 mL of phenyl-GeCl3, 0.6 mL of pentaethyleneglycol monododecyl ether (C12E5), and 5.6 mL of Na (25 w % dispersion intoluene) can be added to a 200 mL flask. This mixture can be stirred forabout 30 minutes, for example, via a magnetic stirrer, and subsequentlytransferred to a Parr reactor. The Parr reactor can be kept at anelevated temperature, e.g., at 280 C, for about 72 hours in a furnacewithout stirring or shaking and then cooled to room temperature.

Germanium nanospheres can then be obtained from a black powder collectedat the end of the above process by washing the powder with excessamounts of hexane, alcohol, and distilled water in order to remove anyNaCl byproducts and hydrocarbon residue. This can be followed by adrying step performed, e.g., in an oven, at 60 C for about 12 hours.Experimental characterizations of prototype Ge nanoparticles synthesizedby the above procedure indicate these particles have crystallinestructure and nanometer sizes, e.g., a diameter of about 20 nm. Asimilar approach can be utilized for synthesizing silicon nanoparticles.In preferred embodiments, the above synthesis steps are preferablyperformed under an inert atmosphere, e.g., an atmosphere of argon, so asto inhibit formation of surface oxide layers that can degradethermoelectric properties of nanocomposite materials generated byemploying the nanoparticles, as discussed in more detail below.

The above wet chemistry approach can also be utilized to formnanoparticle having a core portion surrounded by a shell, such as theabove nanoparticle 11 shown schematically in FIG. 4. For example, ananoparticle having a germanium core and silicon shell can besynthesized by forming Ge core first, and subsequently the Si shell inGe— and Si— containing solution respectively.

As another example, PbSe nanoparticles can be synthesized by utilizing awater-based wet chemistry protocol described briefly below. For example,in one embodiment, 50 milliliter of water can be mixed with 50 mg of asurfactant, e.g., PEG, and 1.3 grams of sodium hydroxide (NaOH). To thismixture, 78 mg of Se and 378 mg of lead acetate, i.e.,Pb(CH₂COOH)₂.3H₂O, can be added. This is followed by adding a reducingagent (e.g., N₂H₄.H₂O) to the mixture while stirring it. The mixture canthen be held in a pressure vessel at a temperature of about 100 C forabout 18 hours, and the resultant material can be washed withwater/ethanol to obtain PbSe nanoparticles having average diameters ofabout 28 nm. The above volumes and masses of different reagents aregiven for illustrative purposes, and those having ordinary skill in theart will appreciate that other values can also be employed.

In another example, PbTe nanoparticles can also be synthesized in asimilar manner. For example, in one approach, 50 milliliter of water canbe mixed with 50 mg of a surfactant, e.g., PEG, and 2.4 grams of sodiumhydroxide (NaOH). To this mixture, 127 mg of Te and 420 mg of leadacetate, i.e., Pb(CH₂COOH)₂.3H₂O, can be added. This is followed byadding a reducing agent (e.g., N₂H₄.H₂O) to the mixture while stirringit. The mixture can then be held in a pressure vessel at a temperatureof about 160 C for about 20 hours, and the resultant material can bewashed with water/ethanol to obtain PbTe nanoparticles having averagediameters of about 10 nm. The above volumes and masses of differentreagents are given for illustrative purposes, and those having ordinaryskill in the art will appreciate that other values can also be employed.

In some cases, vapor phase deposition techniques can be employed forsynthesizing nanoparticles and nanowires needed for fabricatingnanocomposite materials according to the teachings of the invention. Forexample, in one approach, vapor phase deposition can be utilized forsynthesizing Si nanowires and nanoparticles. For example, FIG. 9schematically illustrates a system 46 for synthesizing Si nanowires andnanoparticles via vapor phase deposition, which includes a graphite boat48 with one small opening at each end thereof that is placed in afurnace 50. A source material, e.g., silicon monoxide or silane gas(SiH₄) (e.g., 99.5%), is disposed at a higher temperature end of theboat. The system can then be evacuated to a low pressure, e.g., 0.01Torr, by a pump, e.g., a rotary pump, and a flowing carrier gas (e.g.,argon with high purity mixed with 50% hydrogen) can be introduced intothe boat from one end. In this exemplary embodiment, the gas flow rateis selected to about 100 sccm and the pressure is kept at about 100Torr. Those having ordinary skill in the art will appreciate that othergas flow rates can also be employed. The system can be heated to about135° C. at the source position and held at this temperature for aboutone hour. The gas flow carries vapor from the source downstream portionof the tube to be deposited on a substrate, e.g., a silicon substrate,held at a lower temperature than that of the source (e.g., at 1100 C),to initiate the growth of silicon nanowires and nanoparticles.

After completion of the growth process, the silicon structures can besoaked in a solution of hydrofluoric acid (HF) having a concentration ofabout 10% to remove oxide layers, if there are such layers, and obtainsilicon crystal silicon nanowires and nanoparticles. Scanning electronmicroscopy (SEM) images of prototype silicon structures formed accordingto the above procedure show a plurality of substantially uniformed-sizedsilicon nanoparticles and a plurality of nanowires formed betweenadjacent nanoparticles. And selected area electron diffraction (SAED)spectra show that the nanoparticles are composed of a crystalline coreand an amorphous outer layer. Application of a HF solution having aselected concentration, e.g., about 10%, to these silicon-knottednanowires can result in obtaining free-standing silicon nanoparticles.Alternatively, the silicon nanowires can be utilized.

Segmented and coaxial nanowires constitute other building blocks neededfor synthesizing nanocomposite compositions according to someembodiments of the invention, such as the compositions 26 and 36described above. Various techniques are known in the art for generatingsuch nanowires. For example, in order to synthesize segmented nanowireshaving Si and Ge segments, a vapor phase deposition system, such as theabove system 46, with a Si source and a Ge source can be employed. Thesources can be activated in an alternating fashion to deposit segmentednanowires on a substrate placed downstream of the sources. In anotherexample, PbSe/PbTe segmented nanowires can be fabricated viaelectrodeposition onto an alumina (Al₂O₃) template. Aqueous depositionbaths having lead acetate as a source for lead, and SeO₂ and TeO₂ assources of selenium and tellurium, respectively, can be employed. Thealumina template can be transferred back and forth between the twocorresponding deposition baths, and the deposition potentials can becycled accordingly. For generating coaxial wires, once nanowires of onetype, e.g., silicon, are formed on the substrate in a manner describedabove, the other source, e.g., a Ge source, can be activated to coat thefirst wires with a shell, e.g., a shell of Ge.

In one exemplary method according to the teachings of the invention, thenanoparticles and the nanowires are compacted at an elevated temperatureand under compressive pressure to synthesize a nanocompositecomposition, such as those described above. By way of example, a plasmapressure compaction apparatus 52, schematically depicted in FIG. 10, canbe employed for this purpose. Two graphite pistons 54 and 56 apply ahigh compressive pressure, e.g., a pressure in a range of about 10 toabout 1000 MegaPascals (MPa), to a nanoparticles mixture disposed withina graphite cylinder 58, while a current source 60 provides a currentdensity flow through the mixture for heating thereof. In manyembodiments, the current density is in a range of about 1000 A/cm² toabout 2000 A/cm². The temperature of the mixture, or an estimatethereof, can be obtained by measuring, for example, the temperature ofthe graphite cylinder via an optical pyrometer (not shown) or athermocouple attached to the sample surface. The temporal duration ofthe applied pressure as well as the temperature of the mixture whileunder pressure are selected so as to cause formation of a nanocompositecomposition of interest while inhibiting formation of a homogeneousalloy consisting of the semiconductor components in the mixture.

For example, for forming a nanocomposite material comprising Siinclusions in a Ge host and one consisting of a mixture of Si and Genanoparticles, a powder mixture of Si and Ge nanoparticles can be placedunder a compressive pressure of about 127 MPa while flowing a currentthrough the powder. The current can be increased in steps of 200 A everytwo minutes until the temperature of the mixture reaches about 850 C.The mixture is then held at this temperature under the compressivepressure for about 5 minutes, and subsequently cooled down, e.g., viawater cooling of the pistons, over a period of 1 to 2 minutes.Typically, for generating Si/Ge nanocomposites, the temperature of themixture under pressure is held below the melting temperature ofgermanium.

By way of example and to illustrate the efficacy of the above methodsfor generating thermoelectric nanocomposite materials according to theteachings of the invention, FIG. 11 presents X-ray diffraction datacorresponding to two prototype nanocomposite samples, herein designatedas samples A and B, generated by incorporating nano-sized siliconinclusions in a germanium host matrix in comparison with similar datafor a silicon sample, a germanium sample, and a sample composed of apowder mixture of silicon and germanium. This exemplary data providesclear evidence of two compositions within the nanocomposite samples.

Thermoelectric nanocomposite materials of the invention canadvantageously find applications in both refrigeration and powergeneration. For example, they can be utilized in thermal management ofmicroelectronics and photonic devices. Further, they can be employed asthermoelectric power generators for direct conversion of thermal energyto electrical energy at a high efficiency. By way of example, FIG. 12schematically depicts a thermoelectric cooler 60 formed as an assemblyof thermoelectric elements, such as modules 62 and 64. The elements areelectrically connected in series (or a combination of serial andparallel connections depending on the needs and power supplies) withcurrent flowing alternatively through p-type and n-type legs (formed ofdoped nanocomposites of the invention). The legs of the devices areconnected through electrically conductive bridges to adjacent legs in acascading fashion. Application of a current through the modules causestransfer of heat from one side of the thermoelectric cooler to theother, thereby lowering the temperature at one side while increasing thetemperature at the opposed side.

Alternatively, as shown in FIG. 13, heat can be applied to one side of athermoelectric device 66 having n-type and p-type portions—connected viaan electrically conductive bridging segment—to generate an electricalvoltage across those portions.

Those having ordinary skill in the art will appreciate that variousmodifications can be made to the above embodiments without departingfrom the scope of the invention.

1-13. (canceled)
 14. A method of synthesizing a thermoelectricnanocomposite semiconductor composition, comprising generating a powdermixture comprising two or more sets of nano-sized semiconductorstructures, and applying a compressive pressure to said mixture whileheating the mixture to a selected temperature for a time durationselected to cause compaction of said sets of nano-sized structures intothe thermoelectric nanocomposite semiconductor composition having amatrix with nano-sized inclusions.
 15. The method of claim 14, whereinsaid compressive pressure is in a range of about 10 to about 1000 MPa.16. The method of claim 14, wherein said nano-sized structures aresemiconductor nanoparticles and the semiconductor nanoparticles of oneset have a different composition from the semiconductor nanoparticles ofanother set.
 17. The method of claim 14, wherein the nano-sizedinclusions have a size of 1-300 nm.
 18. The method of claim 17, whereinthe nano-sized inclusions have a size of 1.100 nm.
 19. A method ofsynthesizing a thermoelectric nanocomposite semiconductor composition,comprising generating a powder mixture comprising two or more sets ofnano-sized semiconductor structures, and applying a compressive pressureto said mixture while heating the mixture to a selected temperature fora time duration selected to cause compaction of said sets of nano-sizedstructures into the thermoelectric nanocomposite semiconductorcomposition, wherein said compressive pressure and said time durationare selected to substantially inhibit formation of a homogenous alloycomposed of materials forming said nano-sized structures whilefacilitating formation of the nanocomposite semiconductor composition.20. The method of claim 19, wherein said compressive pressure is in arange of about 10 to about 1000 MPa.
 21. The method of claim 19, whereinsaid nano-sized structures are semiconductor nanoparticles and thesemiconductor nanoparticles of one set have a different composition fromthe semiconductor nanoparticles of another set.
 22. A method ofgenerating a thermoelectric nanocomposite semiconductor composition,comprising: generating a powder mixture comprising at least two sets ofnanoparticles, wherein at least one set is formed of a hostsemiconductor material and at least another set is formed of aninclusion semiconductor material, and applying a compressive pressure tosaid mixture while heating the mixture to a selected temperature so asto cause compaction of said mixture into the thermoelectricnanocomposite semiconductor composition having said inclusionnanoparticles distributed in a host matrix formed of said hostsemiconductor material, wherein said inclusion particles in thenanocomposite are nano-sized.
 23. The method of claim 22, wherein saidcompressive pressure is in a range of about 10 to about 1000 MPa. 24.The method of claim 22, wherein the host semiconductor material isdifferent from the inclusion semiconductor material.
 25. The method ofclaim 22, wherein the nano-sized inclusion particles have a size of1-300 nm.
 26. The method of claim 25, wherein the nano-sized inclusionparticles have a size of 1-100 nm.